ChemInform Abstract: Manganese‐Catalyzed Substitution of Activated Aryl Halides (X: Cl, Br, and F) and Aryl Ethers by Organomagnesium Reagents.

Cahiez, Gérard; Lepifre, Franck; Ramiandrasoa, Parfait

doi:10.1002/chin.200013052

Cited by 13 publications

(28 citation statements)

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“…The use of manganese salts has been scantily reported for the coupling of aromatic halides with Grignard reagents [91,92]. On the other hand, the oxidative crosscoupling of aryl or alkenyl Grignard reagents catalyzed by manganese salts is noteworthy [93] (Scheme 5.25).…”

Section: Manganese-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

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Carbon–Carbon‐Bond‐Forming Reactions Mediated by Organomagnesium Reagents

Chemla

Ferreira

Pérez‐Luna

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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IntroductionFirst reported at the beginning of the twentieth century [1], organomagnesiums are very important synthetic tools. In the field of coupling reactions, first examples of transition-metal-mediated reactions have been reported by Gilman and Lichtenwalter [2] with the oxidative homo-coupling of aryl Grignard reagents in the presence of transition metal halides as both catalyst precursors and oxidants. This reaction was later greatly improved by Kharasch [3], who showed that an efficient homo-coupling reaction could be observed with a small amount of CoCl 2 (3 mol%) and an organic halide as a stoichiometric oxidant. This breakthrough was then followed by the report in 1941 on cross-coupling reactions of arylmagnesium bromides with vinylic halides in the presence of various transition metal salts by the same group [4]. Surprisingly, this seminal work remained mainly unexploited, until this reaction was reinvestigated by several groups in the beginning of the 1970s [5]. Thus, Kochi and Tamura [6, 7] described in 1971 the use of Fe(III) salts as catalyst precursors for cross-coupling reactions, while Kumada [8] and Corriu [9] reported the use of nickel for similar transformations [10,11]. At the same time, the group of Normant [12] described the Cu-catalyzed reaction of the Grignard reagents with organic halides, followed by the report of Murahashi [13] on the use of palladium as a catalyst in similar cross-couplings. Most cross-coupling reactions have been performed with unfunctionalized Grignard reagents because no general method for preparing oligofunctional organomagnesium reagents was available. However, the situation is rapidly evolving, thanks to the groundbreaking work of Knochel and coworkers [14] on the preparation of highly functionalized Grignard reagents. In this chapter, the scope and limitations of cross-coupling reactions involving organomagnesium reagents are showcased with select examples from the recent literature with a special focus on functional-group-tolerant procedures. The recent developments of the most challenging transformations including either the use of oligofunctional metallic species or β-hydrogen-containing nucleophiles will be specially highlighted.

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Section: Manganese-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

“…Activated organic electrophiles such as chloro-, fluoro-, or methoxybenzaldimines [91], various nitrogen-heteroaromatic chlorides [92], and chloroenynes [179] …”

Section: Manganese-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

Carbon–Carbon‐Bond‐Forming Reactions Mediated by Organomagnesium Reagents

Chemla

Ferreira

Pérez‐Luna

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

View full text Add to dashboard Cite

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“…Ackermann reported an efficient aryl-aryl coupling by using nickel complexes of air-stable phosphine oxides [30]. Cahiez and Rieke reported organomanganese-catalyzed cross-coupling reactions in the past 10 years [31][32][33][34]. Hoffman determined the stereochemistry of the transmetalation of Grignard reagents to manganese (II) [35].…”

Section: Introductionmentioning

confidence: 98%

Manganese-catalyzed oxidative homo-coupling of aryl Grignard chlorides

Zhou

Xue

2009

Journal of Organometallic Chemistry

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“…We decided to use the MnCl 2 ‐catalyzed cross‐coupling reaction between activated aryl halides and aryl/alkyl Grignard reagents as a starting point for our investigation . In this transformation, o ‐chlorobenzonitrile undergoes a successful coupling reaction with the organomagnesium halides in THF solution with 10 mol‐% of the catalyst . In addition, both o ‐ and p ‐chlorobenzaldehyde N ‐butylimines can be coupled with the Grignard reagents under the same conditions .…”

Section: Introductionmentioning

confidence: 99%

“…In this transformation, o ‐chlorobenzonitrile undergoes a successful coupling reaction with the organomagnesium halides in THF solution with 10 mol‐% of the catalyst . In addition, both o ‐ and p ‐chlorobenzaldehyde N ‐butylimines can be coupled with the Grignard reagents under the same conditions . However, this is a very narrow range of substrates, and it would be interesting to be able to use a wider array of aryl halides in this transformation.…”

Section: Introductionmentioning

confidence: 99%

Manganese‐Catalyzed Cross‐Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

et al. 2017

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Abstract:The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide is a chloride containing a cyano or an ester group in the para position or a cyano group in the ortho position. A range of other substituents gave no conversion of the aryl halide or led to the formation of side products. A broader scope was observed for the Grignard reagents where a variety of alkyl-and arylmagnesium chlorides participated in the coupling. Two radical clock experiments were performed which in both cases succeeded in trapping an intermediate aryl radical. The cross coupling is therefore believed to proceed by a SRN1 mechanism, where a triorganomanganate complex serves as the most likely nucleophile and single electron donor. Other mechanistic scenarios were excluded based on the substrate scope of the aryl halide.

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ChemInform Abstract: Manganese‐Catalyzed Substitution of Activated Aryl Halides (X: Cl, Br, and F) and Aryl Ethers by Organomagnesium Reagents.

Cited by 13 publications

References 1 publication

Carbon–Carbon‐Bond‐Forming Reactions Mediated by Organomagnesium Reagents

Carbon–Carbon‐Bond‐Forming Reactions Mediated by Organomagnesium Reagents

Manganese-catalyzed oxidative homo-coupling of aryl Grignard chlorides

Manganese‐Catalyzed Cross‐Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

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